Certain polyepoxide treated amine modified thermoplastic phenol-aldehyde resins and method of making same



United States fatent O CERTAIN POLYEPOXIDE TREATED AMINE MODI- FIED THERMOPLASTIC PHENOL-ALDEHYDE RESINS AND METHOD OF MAKING SAME Melvin De Groote, St. Louis, and Kwan-Ting Shen, Brentwood, Mo., assignors to Petrolite Corporation, Wilmington, DeL, a corporation of Delaware No Drawing. Original application February 24, 1953, Serial No. 338,573, now Patent No. 2,771,435, dated November 20, 1956. Divided and this application May 1, 1956, Serial No. 582,042

14 Claims. (Cl. 260-53) The present invention is a continuation-in-part of our copending application, Serial No. 305,079, filed August 18, 1952, now abandoned, and a division of our copending application Serial No. 338,573, filed February 24, 1953, now Patent No. 2,771,435.

Our invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type and particularly petroleum emulsions. Our invention is also concerned with the application of such chemical products or compounds in various other arts and indus tries as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification. The products of our invention are obtained by the method of first condensing certain phenol-aldehyde resins, hereinafter described in detail, with a basic non-hydroxylated secondary monoamine, having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and formaldehyde, which condensation is followed by reaction of the resin condensate with certain phenolic polyepoxides, also hereinafter described in detail, and cogenericallyassoelated compounds formed in the preparation of the polyepoxides.

In preparing diepoxides or the low molal polymers one does usually obtain cogenerie materials which may include monoepoxides. However, the cogenericmixture is invariably characterized by the fact that there is on the average, based on the molecular weight, of course, more than one epoxide group per molecule.

A more limited aspect of the invention is represented by the reaction product of (A) an amine-modified phenolaldehyde resin condensate as described, and (B) a member of the class of (1) compounds of the following formula and (2), cogenerically associated compounds formed in the preparation of (1) preceding.

ice

' 2 kept in mind. The epoxides, and particularly the diepoxides may have no connecting bridge between the phenolic nuclei as in the case of a diphenyl derivative or may have a variety of connecting. bridges, i. e., divalent linking radicals. Our preference is that either diphenyl compounds be employed or else compounds where the divalent link is obtained by the removal of a carbonyl oxygen atom as derived from a ketone or aldehyde,

If it were not for the expense involved in preparing and purifying the monomer we would prefer it to any other form, i. e., in preference to the polymer or mixture of polymer and monomer.

Stated another way we would prefer to use materials of the kind described, for example in U. S. Patent-2,530,353, dated November 14, 1950; Said patent describes cortipounds having the general formula 1 wherein R is an aliphatic hydrocarbon bridge, each n independently has one of the values 0 and 1, and X is an alkyl radical containing from 1 to 4 carbon atoms.

The list of patents hereinafter referred to in the text asfar as polyepoxide goes is as follows:

U. S. Patent No. Dated Inventor- Schater. Mikeska eta]. Do. Do. Cohen et al Rosen et al Rosen. Brltton et a1. Winning et a1. De Groote et al. Swern et a]. February 15, 1949- Wyler.

. ..do Do.

September 27, 1949.--. Dletzler. November 15, 1949 Mlkeska et a1. April 4, Dietzleret al. April 11, 1950 Bock et al. May 2, 1950--. Benderet a1; July 18, 19 Stevens et a];

.do Do.

do Do. October 17, 1950. Dietzler November 14, Havens. August 14, 1951... De Groote et al.- November 20, 1951...- Newey et January 8, 1952 Zech.

January 22, 1952 Greenlee.

The compounds having two oxirane rings and employed for combination with the reactive amine-modified phenolaldehyde resin condensates as herein described are compounds of the following formula and cogenerically assothe divalent groups other than epoxide and hydroxyl groups.

3 radical, the divalent sulfone radical, and the' divalent monosulfide radical S, the divalent radical -CH SCH and the divalent disulfide radical S4; and R is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol R!!! R, I! in which R, R" and R' represent a member of the class of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over -18 carbon atoms; 21 represents an integer selected from alcohols,- ketones, esters, ethers, mixed solvents, etc.

' oxyalkylating agent gives a product which Reference to solubility is merely to differentiate from a reactant which is not'soluble and might be not only insoluble but also infusible. factor insofar that it is sometimes desirableto dilute .the

Furthermore, solubility is a (condensate) compound containing the epoxy rings before reacting with amine. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as for example, kerosene, benzene, toluene, dioxane, various ketones,'chlorinated solvents, dibutyl ether, dihexyl ether, ethyleneglycol diethylether, 'diethyleneglycol diethylether, and dimethoxytetraethyleneglycol.

The expression "epox'y is not usualy limited to the 1,2- epoxy ring. The l,2-epoxy ring issometimes referred to as the oxirane ring to distinguish it from other epoxy rings. otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, Where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2- epoxide rings or oxirane rings in the alpha-omega position. This is a departure, of course, from the standpoint of strictly formal nomenclature as in the example of the Y simplest diepoxide which contains at least 4 carbon atoms and is formally'described as 1,2-epoxy-3,4-epoxybutane l,2-3,4 diepoxybutane).

It well may be that even though the previously suggested formula represents the principal component, 'or components, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described ascomplex resinous epoxides which are polyether derivatives of polyfhydric phenols containing an average of more than one epoxide group per molecule and free from functional U. S. Patent No. 2,494,295, dated January 10, 1950, to Greenlee. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule Hereinafter the word epoxy unless indicated- See and may be entirely free from a hydroxyl group. This is important because the instant invention is directed rings as depicted in the last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any amine-modified phenol-aldehyde resin by virtue of the fact that there are always present reactive hydroxyl groups which are part of the phenolic nuclei and there may be present reactive hydrogen atoms attached to a nitrogen atom, or an oxygen atom, depending on the presence of a hydroxylated group or secondary amino group. a a 1 To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a mole of the oxyalkylating agent, i. e., the compound having two oxirane rings and an amine condensate. Proceeding with the examplepreviously described it is obvious the reaction ratio of two moles of the amine condensate to one mole of the may be indicated as follows:

in which the various characters have their previous significance and the characterization condensate" is simply an abbreviation for the condensate which is described in greater detail subsequently.

Such final product in turn also must be soluble but solubility'is not limited to an organic solvent but may include water, or for that matter, a solution of water containing an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, etc. In other words,the nitrogen groups present, whether two or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base (combination with water) or a salt form suchas the acetate, chloride, etc. The purpose in this instance is to differentiate from insoluble resinous materials,' particularly those resulting from gelation or cross-linking. Not only does this property serve to differentiate from instances where an insoluble material is desired,but also serves to emphasize the fact that in manyinstances the preferred compounds have distinct water-solubility or are distinctly dispersible in 5% gluconic acid. For instance, the prodto add a small amount of acetone to the xylene-methanol V mixture for instance, 5% to 10% of acetone.

The polyepoxide-treated condensates obtained in the manner described are, in turn, oxyalkylation-susceptible and valuable derivatives can be obtained by further reaction with ethylene oxide, propylene oxide, ethylene imine, etc.

Similarly, the polyepoxide-derived compounds can be reacted with a product having both a nitrogen group and a 1,2-epoxy, group, such as 3-dialkylaminoepoxypropane.

,See U. 8. Patent No. 2,520,093, dated August 22, 1950, to Gross.

Although the herein described products have a number of industrial applications, they are of particular value forresolving petroleum emulsions of 'theiwater-in-oil type that are commonly referredito as 'cut oil, roily oil,

emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing of building stone and brick; as wetting agents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents, as, for example for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

As far as the use of the herein described products goes for purpose of resolution'of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in the form of the free base or hydrate, i, e., combination with water or particularly in the .form of a W molal organic acid salt such as the gluconates or the acetate or hydroxy acetate, have .sufiiciently hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 19.50, to DeGroote et al. In said patent such test for emulsification using awaterinsoluble solvent, generally xylene, is described as an index of surface activity.

In the present instancethe various condensation products as such or in the form of the free base or inkthe form of the acetate,.may not necessarily be xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made bysimply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or alow molal alco hol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience what is said hereinafter will be divided'into nine parts with part 3, in turn, being divided into three subdivisions:

Partl is concerned with our preference in regard to the polyepoxide and particularly the diepoxidereactant;

Part 2 is concerned with certain theoretical aspects of diepoxide preparation; Part 3, subdivision A, is of monomeric diepoxides, including TableI;

Part 3, subdivision B, is concerned with the preparation of low molal polymeric epoxides or mixtures containing low molal polymeric epoxides as well as the monomer and includes Tables 11; V 1

Part 3, subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation; 7

Part 4 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation re action to yield the amine-modified resin; 7

Part 5 is concerned with appropriate basic secondary amines free troma hydroxyl radical which maybe employed in the'preparation of the herein-described aminemodified resins; p

Part 6 is concerned with reactions involving the resin,

the amine, and formaldehyde to produce specific-products or compounds which are then subjected to reaction with polyepoxides;

concerned with the preparation bysuchreaction. Generally speaking, this involves nothing more than a reaction between 2 moles of a previously prepared amine-modified phenol-aldehyde resin condensate as described, and one mole of a polyepoxide so as to yield a new and larger resin molecule, or comparable product;

Part 8 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products; and

Part 9' is concerned with uses for the products herein described, either as such or after modification, including any applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART 1 As Will be pointed out subsequently, the preparation of polyepoxides may include the formation of a small amount of material having more than two epoxide groups per molecule. If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are not solventvsoluble liquids or low-melting solids- Indeed, they tend to form thermosetting resins or insoluble materials. Thus, the specific objective by and large is to produce diepoxides as free as possible from any monoepoxides and as free as possible from polyepoxides in which there are more than two epoxide groups per molecule. Thus, for practical purposes what is said hereinafter is largely limited to jpolyepoxides in the form of diepoxides.

As has been pointed out previously one of the reactants employed is a diepoxide reactant. Itv is generally obtained from phenol (hydroxybenzene) or substituted phenol. The ordinary or conventional manufacture of the epoxides usually results in the formation of a cogeneric mixture as explained subsequently. Preparation of the monomer or separation of the monomer from the remaining mass of'the co-generic mixture is usually-expensive. If monomers were available commercially at a'low cost, or if they could be prepared without added expense for separation, our preference would be to use the monomer. Certain monomers have been prepared and described in the literature and will be referred to subsequently. However, from a practical standpoint one must weigh the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint; thus, we have found that one might as well attempt to prepare a monomer and fully recognize that there may be 1 the materials which are most apt to be used for practical illustrate one class.

reasons are either monomers with some small amounts of ploymers present or mixtures'which have a substantial amount of polymers present. Indeed, the mixture can be prepared free from monomers and still be satisfac- V tory. Briefly, then, our preference is to use the monomer or the monomer with the minimum amount of higher polymers.

It has been pointed out previously that the phenolic nuclei in the epoxide reactantmay be directly united, or united through a'variety of divalent radicals. Actually, it is our preference to use those which are commercially available and for most practical purposes it means instances Where thephenolic nuclei are either united directly without any intervening linking radical, or else united by a ketone residue or formaldehyde 'residue' The commercial bis-phenols available now in the open market The diphenyl derivatives illustrate a second class, and the materials obtained by reacting substituted monofunctional phenols with an aldehydeillusvtrate the third class. All the various known classes may be used but our prefernce rests with these classes due to Part ,7 is concerned with the reactions involving the their availabilityand ease of preparation, and also due to the fact :that thecost is lower than in other examples.

Although the diepoxide reactants can be produced in more than one way, as pointed out elsewhere, our pref- 'erence is to produce them by means of the 'epichloroof'the following structure is preferred as the epoxide reactant and will be used for illustration repeatedly with the full understanding that any of the other epoxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures of the monomer and higher polymers are satisfactory. -The formula for this compound is I Reference has just been made to bis-phenol A and a 7 suitable epoxide derived therefrom. Bis-phenol A is dihydroxy-diphenyldimethyl methane, with the 4,4 isomers predominating and with lesser quantities of the 2,2 and 4,2 isomers'being present. It is immaterial which one of these isomers is used and the commercially available mixture is entirely satisfactory.

Attention is again directed to' the fact that in the instant part, to wit, PART ONE, and in succeeding parts, the text is concerned almost entirely'with'epoxides in which there is no bridging radical orthebridging radical is derived from an aldehyde or a ketonef It would be immaterialif the divalent linking radical would be derived from the other groups illustrated for the reason that nothing more than mere substitutionof one compound for the other would be required. Thus, what is said hereinafter, although directed to one class or a few classes, ap plies with equal force and effect to the other classes of epoxide reactants;

If sulfur-containing compounds are prepared they should be freed from impurities with considerable care for the reason that any time that a loW-molal sulfur-containing compound can react with epichlorohydrin there may be formed a by-product in which the chlorine happened to be particularly reactive and may represent a product, or a mixture of products, which would be unusually toxic, even though in comparatively small concentration.

-PART 2 Treatment with epichlo-rohydrin, for'example, does not yield this product initially but there is an intermediateproduced which can be indicated by the following structure:

,CHa V, v I. HV-H H GIG H.H ,H.. HCCCO o o-o-o-ou I I H l H I I 01 H CH3 on 01 .1 Treatment with alkali, of course, forms the epoxy ring. A number of problems are involved in attemptingto produce this compound free from cogeneric Y materials of related composition. The difliculty stems from a number of sources and a few of the more important ones are as follows:

(1) The closing of the epoxy ring involves 'the use of caustic soda or the like which, in turn,"is anetfective catalyst in causing the to open an' oxyallsylation reaction."

Actually, what. may happen for any one of a number OH OH (2) Even if one starts with the reactants in the preferred ratio, to wit, two parts of epichlorohydrin to one part of bis-phenol A, they'do not necessarily so react and as a result one may obtain products in which more than two epichlorohydrin residues become attached to a single bis-phenol A nucleus byvirtue of'the reactive hydroxyls present which enter into oxyalkylation reactions rather than ring closure reactions. A

' (3) As is well known, ethylene oxide in the presence of alkali, and for that matter in the complete absence of water, forms cyclic polymers; Indeed, ethylene oxide can produce a solid polymer. This same reaction can, and at times apparently does, take place in connection with compounds having one, or in the present instance, two-substituted oxirane rings, i. e., substituted 1,2 epoxy ringsl Thus, in many ways it is easier to produce a polymer, particularly a mixture of the monomer, dimer and trimer, than it is to produce the monomer alone.

(4) As has been pointed out previously, monoepoxides may be present and, indeed, are almost invariably and inevitably present when one attempts to produce polyepoxides, and particularly diepoxides. The reason is the one which has been indicated previously, together with the fact that in the ordinary course of reaction a diepoxide, such as may react with 'a mole of bis-phenol A to give a monoepoxy structure. Indeed, in the subsequent text immediately following reference is made to the dimers, trimers and tetramers in which two epoxide groups are present. Needless to say, compounds can be formed which correspondin every respect except that one terminal epoxide group is absent and in its. place is' a group having one chlorine atom and one hydroxyl group, or else two hy droxyl groups, or an unreactedphenolic ring;

- (5) Some reference has been made to the presence of a chlorine atom and although all effort isdirected towards the elimination of any chlorine-containing molecule yet it is apparent that this is often an ideal approachrather than a practical possibility. Indeedfthe same sort of reactants aresometimesemployed to obtain productstin which intentionally there. is both an epoxide group and a chlorine atom present. See U. S. .Patent No.

2,581,464, dated January 8, 1952, to Zech.

.For purpose of brevity, without going any further,

7 the next formula is in essence one which,'perhaps in an idealized way, establishes 'the composition of resinous products available ,under the name of Epon Resins as now sold in'the openmarket. See, also, chemical pamphlet entitled fEpon Surface-Coating Resins, Shell Chem- CH; DH CH:

For the purpose of the instant invention, n may repre- 10 pounds where, instead of the oxirane ring '(1,2-epoxy sent a number including zero, and at the most a low ring) there is present a 1,3-epoxy ring. Such comnumber such as 1, 2 or 3. This limitation does not exist pounds are derivatives of trimethylene oxide rather than in actual efforts to obtain resins as differentiated from ethylene oxide. See U. S. Patents Nos. 2,462,047 and the herein described soluble materials. It is quite prob- 2,462,048, both dated February 15, 1949, 'toWyler.

able that in the resinous products as marketed .for coat- In summary then in light of what has been said, coming use the value of n' is usually substantially higher. pounds suitable for reaction-with amines may be sum- Note again what has 'beensaid previously "that any 'formarizedby-the following formula:

l m on Liz!!! I I I I mula is, at best, an over-simplification, or at the most or for greater simplicity the formula could be restated represents perhaps only the more important or principal thus: I

Hz H H: H2 H2 constituent or constituents. These materials may vary in which theyarious characters have their prior signififrom simple non-resinous to complex resinous epoxidescance and in which R 0 is the divalent radical obtained which are polyether derivatives of polyhydric phenols by the elimination of a hydroxyl hydrogen atom and '21 containing an average of more than one epoxide group nuclear hydrogen atom from the phenol per molecule and free from functional groups other than 40 epoxide and hydroxyl groups. Referring nowto what has been said previously, to wit, Y

compounds having both anepoxy ring or the equivalent I and also a hydroxyl group, one need go no further than to consider the Ramon product of in which R, R", and R' represent a member of the CH; class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member H I H I having not over 18 carbon atoms; n represents an integer 0 OH 0 t I selected from the class of zero and 1, and n represents a and bisphenol A in a mole-for-mole ratio, since the initial Whole number not than reactant would yield a product having an 'unreacted epoxy PART 3 ring and two reactive hydroxy radicals. Referringagain I a S ubdzwszon A to a previous formula, consider an example where .two moles of bisphenol A have been reacted with 3 moles The preparations of the diepoxy derivatives of the diof epichlorohydrin. The simplest compound formed phenols, which are sometimes referred to as diglycidyl would be thus: ethers, have been described-ma number of patents. For

' CH3 on CH; ogtgmmmmgtgo l l H: CH: 7 H! CH: a. I H l O 1 l i 0 j, Y,

Such a compound is comparable to other compounds convenience, reference will be made to two only, to wit, having both the hydroxyl and epoxy ring such as 9,10- aforementioned U. S. Patent 2,506,486, and aforemenepoxy octadecanol. The ease with'which this type of' tioned UsSiPa'tent'No.2,530,353. compound polymerizes is pointed out by U. S. Patent Purely by way of illustration, the following diepoiddes, No. 2,457,329, dated December2-8, 1948,10 Swern etal. ondiglycidylethers ,as they are sometimes termed, are The same difficulty which involves the tendencygto included for purpose of "illustration. 'These particular polymerize on the part of compounds having a reactive ring and a hydroxyl radical may be illustrated by comtioned.

compounds are described in the two patents just men- TABLE I Ex- Patent ample Dlphenol Diglycidyl ether refernumber 7 a once CH2 05114011); Di(epoxypropoxyphenyl)methane 2, 506, 486 CH; H(C6H4OH)1-- Di(epoxypropoxyphenyl)methylmethane 2, 506, 486 (CHs)zC(CuH OH)2 Di(epoxypropoxyphenyl)dimethy1methane 2, 506, 486 OQHEO (0H3) (C H4OH); Di(epoxypropoxyphenyl)ethylmethirlmethane- 2, 506, 486

GgHs)zC(CaH4 z--- Di(epoxypropoxypheny1)diethylmethane 2, 506, 486

H3O(C3H (05114011): Di(ep0xypropoxyphcny])methylpropylmethanei1 2, 506, 486 (EH30 (C 115) (CsH4OH)z Di(epoxypropozryphenyl)methylphenylmetlmne 1 2, 506, 486 C7H50(-CH5) (G H oHhu Di(epoxy propoxyphenyl)ethylphenylmethane.. 2,506,486 C H C(OuH5)(CaH4OH)g Di(epoxypropoxyphenyl)propylphenylmethane 2, 506, 486 C H C(OtH5) (C'uH4OH Dl(epoxypropoxyphenyl) butylphenylmethane 2, 506, 486 (CH OH4)GH(C H4OH)2 Di(epoxypropoxyphenyl)tolylmethane 2, 506, 486

CH3C5H4) 0 (CH3) (051140 Di (epoxypropoxyphenyl) tolylmethylmethanei 2, 506; 486 Dihydroxy diphenyL. 4,4-bis(2,3-epoxypropoxy)diphenyl 2; 530, 353 7 (CH3)C(G4H5.C0H3O 2,2-bis(4-(2,3-ep0xyprcpoxy)2-tertiarybutyl phenyl)propa.ne. 2, 530, 353

V V Y Subdivision B As to the prepara tionof low-molal polymerieeporrides or mixtures reference is made to numerous patents and 20 to the formula thel'filfl Provlded 0116 Still bears in mmd particularly the aforementioned U. S. Patents Nos. 2,575,-

In light of the aforementioned U. PatentNo. 2,575,- 55 8, the following examples can be specified by reference it is in essence an over-simplification.

558 and 2,582,985.

' TABLE II 5 i oo 'o OR [R],.R1OCC-C- -OR1-[R],, RrOCO-C H: H H2 H2 H2 H, E E3 1 I (in which the characters have their previous significance) Example R O--from HR OH" FR JTLQ l2 1 "n' Remarks 1 number B1 Hydroxy benzene 7 CH3 1 1 0,1,2 Phenol lmown as bis-phenol A. Low a a l1 polymeric mixture about 3:; orrmore C where n=0, remainder largely wherev I 'n=1, some where n'=2. CH; 7 1 B2 do CH; 1 0,1,2 Phenolknownasbis-phenolB. ,Seenote regarding B1 above.

i V V a r CH3 no B3 Orthobutylphenol OH; 1 0, 1, 2 Even though 71' is preferably 0, 'yet the I usual reaction product might well con- C- V tain materials where n is '1, or to a. I lesser degree 2. q 7 CH5 1 V 1 B4 orthoamylphenoln (13H; 1 r 0, 1,12- "11:330.

C 3 7 l B5 Orthooctylphenol (EH; 1 0,1,2 Do.

1 ,CHs' in Orthononylphenol 3 1 0'12 l; M 1 r CH: B7.'-.'.Q-. Orthododeoylphenolon, 1 0,1,2 Do.

V CH3 if V B8 Metacresol; L CH; 7 1 0,1,2 See prior note. flhis phenol used as 1 1 1 initial materlal is known as bis-phenol -O-- C. For other suitable bis-phenols see I U; s. Patent 2,564,191. CH: 1

B0 ..do l CH: 1 0,1,2 See prior note.

e V 7 CH: 7 v 7 B10 n Dibutyl(ortho-peralphenolr t 1 0,1,2 Do.

B11... .1 Diamyl (ortho-para) phenol- 1 0,1,2 Do. 1f

Y The prior examples "have been limited largely to those in which there is no divalent linking radical, a'sainthe 'case: of 'diphenylcompounds, or where the linking radical is derived from a ketone or aldehyde, particularly a ketone. Needless to say, the same procedure is employed in converting diphenyl into a diglycidly ether regardless of the nature of the bond'between the two phenolic "nuclei. .For purpose of illustration attention is directed to numerous other diphenols which can be readily converted to a suitable polyepoxide, and particularly diepoxide, reactant. I

As previously pointed 'out the initial phenol may be substituted, and the substituent group in turn may be a cyclic group such as the phenyl group or cyclohexyl group as in the instance of cyclohexylphenol or phenylphenol. Such substituents are usually in the ortho posi- "1ABI1lll'1I- ontinued Example -R O from H R iOH R- n 1; Remarks number B12 Dioctyl (ortho para) phenol. H 1 0,1,2 See prior note. This phenol used as I initial material is known as bis-phenol p H C. For other suitable bis-phenols see U. S. Patent 2,564,191.

31s---- Dinonyl(ortho-para)pheno1. at 1 0,1,2 D0.

Bl-t. Diarnyl (ortho-para) phenol. 1(3). 1 0, 1, 2 Do 31 5 do 7 1g 1 0, 1, 2 Do.

01H B10 Hydroxy benzene (i) 1 0,1,2 Do.

Diamyl phenol (ortho-para); ss 1 o, 1, 2 Do. do '-s- 1 0,1,2 Do. 1319..-; Dibutylphenol(ortho-paral. gl i 1 7 0,1,2 7 no.

B do H H 1 0,1,2 Do

. ,1 1 1 s. H B21.. DinonylphenoKortho-para). I '13 r 1 0,1,2 Do

B22 Hydroxy benzene 1 0,1,2 Do.

. C 7 B23 do None 0 0,1,2 Do. B24 Ortho-isopropyl1phenol;;.;--

CH1 1 0,1,2 Seepriornote. (As to preparation of 4,4- isopropylidene bis-(2-isopropylphenol) see U. S. PatentNo. 2,482,748, dated (l: Sept. 27, 1949, to Dietzler.) B 1 .1 s fara-oetylphenol, I; Q- I-TCHZ S-rCH 1 0,1,2 Seepriornote. (As to preparationoi the I phenol sulfide see U. S. Patent No. A 2,488,134, dated NOV. 15, 1949, to p 7 V t Mikeska et a1.) 1826... Hydroxy benzene 7 CH: v 1 0,1,2 Seepriornote. (As to preparation ofthe t I V phenol sulfide see U. S. Patent No.

5 t h s Subdivision C tion and may be illustrated by a phenol of the following composition Similar phenols whichare monofunctional, for instance, ,paraphenyl phenol or paracyclohexyl phenol with an ad- 0 ditional substituent in the ortho position, may be emfor subsequent reaction with epichlorohydrin, etc.

' 1 5 Other examples include:

HI 7 CH3 '10 wherein R is a substituent selected from the class consisting'of secondary butyl and tertiary butyl groups and R is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups, and wherein said alkyl group contains at least 3 carbon atoms. See U.'S. Patent No. 2,515,907.

H(OC2H1)9O 0(CgH4O)nH CsHuOCHrOCsHu CuHu CsHn V '25 in which the -C H groups are secondary amyl groups." f See U. S. Patent No. 2,504,064.

CeHu CaHia H0 OH See U. S. Patent No. 2,285,563. i i

r ar/ C aOCHs C r (3H2 CH-CH: fi -5 CE\[z /CH2 CHE-CH:

See U. S. Patent No. 2,503,196.

EB: h

wherein R is a member of the group consisting of alkyl, and alkoxyalkyl radicals containing from 1 to 5 carbon atoms, inclusive, and aryl' and chloraryl radicals of the benzene series. 'SeeU. S. Patent .No. 2,526,545.

0H 0H 1'1, R1 (|l R1 R2 whereinR is a 'substituent selected from theclass consisting of secondary buty1 and tertiary butyl groupsand R, is a subs'tituentselected from the class consisting of a U.; S. Patent-No. 2,515,906.

cH=oH a I 0H C =CH OH.

1 CH3 CH3 See U. S. Patent No. 2,515,908.

As to sulfides, the following compound is of interest:

See U. s. Patent No. 2,331,448. U

As to descriptions of'various suitable phenol sulfides, reference is madeto the following patents: U. S. Patent Nos. 2,246,321, 2,207,719, 2,174,248, 2,139,766, 2,244,021 and 2,195,539. H

As to sulfones, see U. S. Patent No. 2,122,958.

As to suitable compounds obtained by the use of formaldehyde or some other aldehyde, particularly compounds such as in which R is a methylene radical, or asubstitutcd methylene radical Whichrepre'sents the residue of 'an aldehyde and is preferably the unsubstituted methylene radicalderived from formaldehyde. See'U. S. Patent No.

2,430,002. 'u e P See also US. Patent No. 2,581,919 which describes di(dialkyl cresol) sulfides which include the monosulfides, the disulfides, and the polysulfides. The following formula represents the various dicresol sulfides of this invention:

on" CH; OH: OH

in.,which,R and R arealkyl groups, the sum of whose carbon atoms equals 6 to about 20, and R 'an'd'Rg each preferably 'co nta'in"3 to about '10 carbon atoms,':"andix is 1 to 4.. The term sulfides? as used in this ,text therefore, includes monosnlfide, disulfide, and polysullides PART It is well known that one can readily purchaseon the .open market, or prepare, fusible, organic solvent-soluble,

water-insoluble resinvpolymers of a composition approximated in an idealized form by the formula OH 0H, 1 31 .In --.the above vformula n represents a small heating under a vacuum a ae wholenumber 8, or more, up ,to probably 1.0 when the resin ,is subjected to as described in the literature. A limited sub-genusis in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., it varies from 1 to 4;-R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecylradical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trivarying from 1 to 6, 7 or or 12 units particularly functional phenols aspreviously noted. However, even when obtained from a difunctional phenol, for instance :paraphenylphenol, one may obtain a resin which -is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenatedsolventsuch as a low molaltalcohol, dioxane, or .diethyleneglycol diethylethe'r. Sometimes a mixture of the two solvents (oxygenated and non-oxygenated) will serve. 8% Example 9a of .U. S. Patent N0. 2,499,365, .dated March 7, 1950, to

De Groote and Keiser. I

The resins herein employedas raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to makea-solubility tGStxOfl commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, .1950, to De Groote and'Keiser. In said patent thereare described oxyalkylanon-susceptible, fu.si-.

ble, nonoxygenated-organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resins having an average molecular weight corresponding to at least 3. and not over 6 phenolic nuclei per resin molecule. These resins are 'difunctional only in. regard to methylol-forming reactivity,

are derived by reaction between a difunctionaLmonohydric phenol and an aldehyde having not over-8 carbon atoms and reactive toward said-phenol and .are formed in the substantial absence of trifunctional'phenols. The phenol is of the formula The basic nonhydroxylated amine 'may be designed thus: 3 7

I i. e., one having just 3 units, or just 4 units or weight may be Inconducting ,reactionsof thiskindone doesnot necessarily obtain a hundred percent yield -for obvious reasons. Certain side reactions may take place. 'For'instance, 2 moles of amine may combine with one mole of the aldehyde, or onlyone mole of the amine may combine with the resin molecule,-or even to avery slightcxtent, if at all, 2 resin units may combine without/any amine in the reaction product, as indicated in the following formulas:

As has been pointed out-previously, as far as .theresin .unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehydebr butyraldehyde. The resin .unit may beexemplified thus:

OH 1 OH r// RIII O R n R in which R is the divalent radical obtainedfrorntheparticular aldehyde employed 'toform the resin. For reasons which are obvious the condensation product obtained appears to be described best'interms of "the method of manufacture. V

As previously stated'the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can'be made using an acid catalyst or basic catalyst or a.catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared-by using a strong acid as a'catal yst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found thatsometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent andas much as'a few IOths-of a-percent. Sometimes moderate increase in caustic soda and caustic potash may be used.

However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does notget a single polymer, just 5 units, or just 6 units, etc. It is usually a mixture; "for instance, one approximating 4fp'henolic nuclei will'have some trimer and pentamer present. Tlius,' -'t l1emolecularsuch that it corresponds to -"a"fract'ional value for n'as, for -exa'mple, 3:5, 4;5,*or 5.12.

. "In the actual manufacture'of the resins we 7 reason 'forusing other than those which arelowest (in e 7 price and most readily available commerciallyq fFo 19 poses of convenience suitable resins are characterized in the following table:

TABLE III D/Iol. wt. 'Ex- Position 12' of resin ample R of R derived n molecule number from- (basedon n+2) Phenyl 3. 5 992. 5

Tertiary butyl 3. 5 882. 5 Secondary butyl. 3. 5 882. 5 Cyclohexyl. 3. 5 1, 025. 5 Tertiary amyl 3. 5 959. Mixed secondary 3. 5 805. 5

and tertiary amyl.

' Prop 3. 5 805. 5 Tertiary hexyl 3. 5 1, 030. 5 Octyl 3. 5 1, 190. 5

Nonyl 3.5 1,330.5

' Tertiary butyl 3. 5 V 1, 071. 5

Terti amyl 3. 5 1, 148. 5

Nony li nud 3. 1, 456. 5

' 'Propional- 3. 5 1, 008. 5

. V dehyde. Tertiary amyl do 3. 5 1, 085. Non do 3.5 1,393. Tertiary butyl Formal- 4. 2 996.

' dehyde.

Tertiary amyL do 4. 2 1, 083. Nonyl 4. 2 1, 430. Tertiary butyl. 4. 8 1, 094. Tertiary army]. 4. 8 1, 189. Nonyl 4. 8 1, 570. Tertiary amyl 1. 5 604. Cyclohexyl 1. 5 646. H 1.5 653. 1.5 688.

Hexyl d 2. 0 748. 0

40a Cyclohexyl. do .do 2.0 7 0. 0

PART 5 As has been pointed out previously, the amine herein employed as a reactant is a basic secondary. monoamine,

I and preferably a strongly basic secondary monoamine,

1 The secondary amines most readily available are,-of course, amines such as dimethylamine, methylethylamine,

diethylainine, ,dipropylamine, ethylpropylamine, dibutyl amine, diamylamine, dihexylamine, 'dioctylamine, and

dinonylamine. Otherv amines include bis(1,3-dimethyl-' v For example, one can methylate alpha methylbenzylamine, or

, benzylamineitself, toproducea suitable reactant. Need- ;less to.say, one can use secondary lhxylamihe, dibutylamineor aminescontainingone cyclehexyl group and one alkyl group, or one benzyl group amines such as dicyclocco cooopenacns menu:

1 945, to Jones et a1.

in which is a small whole number having a value of l or more, and may be as much as 10 or 12; n is an integer having a value of, 2 to .4, inclusive; m represents the numeral 1 to 2; and 111" represents a number 0 to l, with the proviso that .thesum' of m plus m equals 2; and'R has its" prior radical.

The preparation of such. amines has been described in the literature and particularly in two United States patents, to wit, U. S. Nos. 2,325,514 dated July 27, 1943. to Hester, and 2,355,337 dated August 8, 1944, to

significance, particularly as a hydrocarbon Spence. The latter patent describes typical haloalkyl ethers such as i CH3OCzH4Cl ou -mu,

CH2 CH-CHaOCaHrOCaH4BI 02 40 CzHaO 01 40 021140 CzHrGl Such haloalkyl ethers can react with ammonia, or with a primary amine such as methylamine, ethylaminc, cyclohexylamine, etc., to produce a secondary amine of the kind above described, in which one of the groups attached to nitrogen is typified by R'.- Such haloalkyl ethers also can be reacted with ammonia to give secondary amines as described in the first of the two' patents mentioned immediately prededing. Compounds so obtained are exemplified by zHt s i z nz u (C H OC H OC H OC H NH a (C H OCH CH(CH O CH CHCH NH (CH OCH CH OCH CH OCH CH NH CH OCH CH CH CH CH gNH Other somewhat similar secondary amines are those of the composition 7 /NH R-0 (CH1): as described in U. S. .Patent No. 2,375,659 dated May 8, In the above formula R may be 1 methyl, ethyl, propyl, amyl, octyl, etc.

butyl)amine. There are, of course, a variety ofprimary ,amines which can be reacted with an alkylating agent; such as ,dimethyl. sulfate, diethyl sulfate, an alkyl bro- -mide, an ester ofsulfonic acid, etc.,.to produce suitable famines' withinthe herein specified limitations. '70

Other amines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or, for that matter, amines of the kind described in U. S. Patent No. 2,482,546 dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examplesfinclude the following: beta-phenoxyethylamine, gamma phenoxypropylamine', beta-phenoxyr alpha-methylethylamine, and beta-phenoxypropylamine.

Other suitable amines are the kind described in British Patent No. 456,517 and may be illustrated by The products obtained by the herein described processes employed in the manufacture of the condensation product represent cogeneric mixtures which are the re- 't ns ate A oth cto a Whether or not the cogenericmixture obtained at the assess:

a resin or in-the manufacture of'a phe nol -amine-aldw hyde resin; or else. from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,551 in orderjto obtain a heatreactive resin: Since th e condensation products obtained are "not heat-convertible and since manufacture is, not restricted to a single phase system, and since temperaobvious that the procedure becomes comparatively simple. Indeed, perhaps no descriptionisnecessary over and above what has been said previously, in light ofsubsequent examples. However, for purpose of clarity the following details areinc luded. j

A convenient piecepf equipment for preparation of these cogeneric mixtures is a resinpot of the lgind decribed in aforementioned U. S. Patent No. 2, 22,95 68. In most. instances theresin selected is not apt to be a fusible liquid at he earlyjonlow temperature stageof reaction if employed as subsequently describedjinjgfact, usually it is apt to be a solid at ordinary or higher temperatures, for instance, ordinary room temperature. Thus, we .have found it convenient to .use a solvent and v particularly one which 'c b removed readily. at a comparatively moderate temperature, for.instance, at 150 C. A suitable solvent is usuallybenzene, xylene, or a comparable petroleum hydrocarbon or. a. mixture .of such or similar solvents. Indeed, resins which are. not soluble except in oxygenated solvents or. mixtures containing suchsolvents are not here included as raw ma- .terials The reaction can be conducted in such a way that theinitialreaction, andperhaps the bulk ofthe reaction, tak p e. i ap h' s t Howe e e i able, one can use an oxygenated solvent such as a lowboiling alcohol including .ethyl alcohol, methyl alcohol,

et is -a h s: .bsdor o an. s a comparatively non-volatile. solvent such as dioxane or the ,diethyletherof ethyleneglycol. One can also usea mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvents isnot re- .quired in the sense that it is not necessary touse an initial resin which issoluble only in an. oxygenated solvent as just noted,v and it is. not necessary .to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the jreason that'in-most cases aqueous formaldehyde is-em- .ployed, which may be the commercial product which is approximately 37%, or it may be diluted-down to about 30% formaldehyde. However,paraformaldehyde can be ;used but it is more difficult perhaps to addasolid material instead;of the liquid solution and, everythingv else being equal, the latter is apt to be more'economical'. In any .event, water is present as water of reaction; Ifthesolvent is completely removed at the endv of the process, no, problem is involved if the material, is used forany subsequent reaction. However, if thereaction mass is .going to be subjected to some furthenreaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if thereis to be subsequent oxyalkylation, then, obviously, the alcohol should not beused -or else it should be removed. The fact that an oxygenated solvent need not beemployed, of course; is an advanfar the selection of lsolvent goes,

tures up to 150 C. or thereaboutsrnay be employed, it a #22 end of -the.reaction. is? t'oi-be ,used; as such or in the salt formf The cogenericmixtures obtained are apt to, he solids or thick viscous liquids .in which there is some change from the initial resin itself, particularly if some Qf the initial solvenLis. apt to remain without complete removal. Even if one starts with a resin which is almost water-white :inlcolor, the products obtained are almost invariably a..dark redin color or at least a red-amber, or some colorv which includes both an amber component and a reddish component; By and large, the melting point is apt to be lowerand .the jproducts may be more sticky and moretacky than-the original resin itself. Dependmg on'the resin selected and on the amine selected the condensation'iproductor reaction mass on a solvent-free basis may be hard, resinous and comparable to the resin itselfl. 1 .,The products obtained, depending on thereactants selected,.rnay bewater-insoluble or water -dispersible, .or

water-so1ub1e,,-.or closeto being water-soluble. Water solubility -is enhanced, of course, by making a solution in the acidifiedvehicle such as a dilutesolution, for in- SiQIlQQgi3.15%.rsOllltlOn:Of' 'hYdI'OChlOI'lC acid, acetic acid, hydroxyacetic ,acid, etc. One, also may convert the finishedproduct into, salts by simply adding a stoichiornetricjamountpf any selected acid andjremoving any waten zpresent by refluxing with benzene or the like. In .fact,:.the.-.$.1ection offthe solventemployed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

Inthe nextsucceeding paragraph it ispointed out that frequently it; is convenient to eliminate all solvent, using ,a temperatureof not, over 150 C. and employing vacuum, iffrequired This applies, of course, only to those circumstances where it is desirable or necessary to remove-the solvent. Petroleum solvents, aromatic solvents, .etc., can be used. The, selection of solvent, such as benz ene,. xylene, or,the,.lik e, depends primarily on cost, i. e., the use of the most economical solvent and also on three other. factors',-,two of which have been previously ment ioned; '(a) is thesolvent to remain in the reaction mass withoutremoval? (b) is the reaction mass to be subjected .to further reaction in which thesolv'ent, for instance, .an galoolg ol, either 'l ow;b.oiling or high boiling, might interfefe as in the case of oxyalkylation); and the third factor .is, this,,(c) is an effort tabernacle to purify, the reaction .m ssby. he;u i1a1 ..p c u a for example, a Water- .wash to remove the water-soluble unreacted formaldehyde if,any,-or; awater-wash to remove any unreacted vvlow molaLsolubleamine, if employed and present after reaction? .Suehprocedures are well known and, needless to say .certai n solvents are more suitable than others.

Everything else being equal, we have found xylene the and for reasons explained, this is not necessary although lit does apply in some other procedures that, ina general way," bear some similarity to the present procedure. lhere is no.objection, of course, to giving the reaction ,anopportunity to proceed as far as it will at some low temperature ffor instance, to 40 but ultimately one must employ thehigh'er temperature inorder to obtain products of the kindh erein described. If a lower temperature, reaction isused initially the period is not critical,.,in, fact, itmay be anythingfrom afew hours up to 2d,.hour s. I We have not found any case where, it was .necessary reVen desirable to hold the low temperature st e. for, more fthan 24.hours.' Infact, we are not con.- vlnceditherelis any advantage in holding it. at this stage for'rnore than 3 or 4 hours at the most. This, again, is a jn'iatter of'convenience largely for one reason. lnheating an ura realc'tion mass there is a tendency ,forzfoirnald ehydetto 'be: lost.- Thus, if the reaction can '23 the amount of unreacted formaldehyde is decreased sub; sequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected'so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain'circumstances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction'probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is in variably the same when adding the resin and the selected solvent, such as benzene or xylene. Refluxing should be long enough to insure that the resin added, preferably in a,powderedfor'rn, is completely soluble. However, if the resin is prepared as such it may be added in solution form, just'as preparation is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the amine isadded and stirred. Depending on the amine selected, it may or may not be soluble in the resinsolution. If it is not soluble in theresin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added,'and if not, it iseven possible that the initial reaction masscould be a three-phase systern instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 3 5 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable forrn. For reasons pointed out we preferto use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

On a large scale if there is any difliculty with formaldehyde loss control, one can use a more dilute form of formaldehyde, for instance, a 30% solution. The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem tags to completion, foaming takes place, and

other mechanical or chemical 'difliculties are involved.

We have found no advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as far as one can reasonably expect at a low temperature; for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or C. for 4 or 5 'hours, or at the most, up to 10-24 hours, we then com- 'plete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of timewhich avoids loss of amine or formaldehyde. At a higher temperature we 'use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We their permit the temperature to rise to somewhere about C., and generally slightly above 100 C., and below 150 C., by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined material was dark redin color and had the range. This period of heating and'refluxing, after the water is eliminated, is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same Way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based onthe molecular weight of the resin molecule, 2 moles of the secondary amine and 2 moles of formaldehyde. In some instances we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage in'this. In other cases we have used a slight excess of amine and, again, have not found any particular advantage in so doing. When ever feasible we have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not the end-product showed surface-activity, particularly in a dilute acetic acid solution. The nitrogencontent after removal of unreacted amine, if any is present, is anotherindex.

Irilight of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration: p 7

Example 1b The phenol-aldehyde resin is the one that has been identified previouslyas Example 2a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which Was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes the two external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the two external nuclei or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a, preceding, were powdered and mixed with an equal weight of xylene, i. e., 882 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 30 C. to 35 C., and 146 grams of diethylamine added. The mixture was stirred vigorously and formaldehyde added slowly. The formaldehyde was used as a 37% solution and 162 grams were employed, which were added in about 2 /2 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 45 C for about 20 hours. At the end of this period of time it was refluxed using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time, and the presence of unreacted formaldehyde noted.

Any unreacted formaldehyde seemed to disappear within 2 to 3 hoursafter refluxing was started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all water of solution and reaction. After the water was eliminated part of the xylene was removeduntil the temperature reached approximately C., or slightly higher. The mass was kept at this higher temperature for about 4 hours and reaction stopped. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylenewas permitted to stay in the cogeneric mixture. A small amount ofthe sample was heated on 'a water bath to remove the excess xylene and the residual consistency *of a sticky fluid or tacky resin. The overall time for the reaction was about 30 hours. Time can be reduced by 25 cutting low temperature period to approximately 3 to 6 hours..

Note that in Table IV following there are a large number of added examples illustrating the same prooxygenated solvent such as the diethylether of ethylene glycol, or the diethylether of propylene glycol, or similar ethers, either alone or incombination with a hydrocarbon solvent. The selection -of the solvent depends in part cedure. In each case the initial mixture was stirred and on the subsequent use of the derivatives or reaction prodheld at a fairly low temperature (30 to 40 C.) for a fucts. If the reaction products are to be rendered solventperiod of several hours. Then refluxing was employed free and it is necessary that the solvent be readily reuntil the odor of formaldehyde disappeared. After the moved as, for example, by the use of vacuum distillation, odor of formaldehyde disappeared the phase-separating thus xylene or an aromatic petroleum Will serve. It is trap was employed to separate out all the Water, both the 10 easy enough to select a suitable solvent if required in any solution and condensation. After all the water had been instance but, everything else being equal, the solvent separated enough xylene was taken out to havethe final chosen should. be the mo t economical one. product reflux for several hours somewhere in the range J x ipfl'e 1c of l45 to 150? C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, r The product was obtained ,by reaction between the dior all of the water, had been removed. 4 epoxlde prevlously'deslgnated' asdlepoxlde 3A, and con- ,Note that as pointed out previousl this procedur is densate 1b. Condensate 1b Wasobtained from resin 2a. illustrated by 24 examples in Table IV. Resin 2a was, obtained-from, tertiary butylphenol and TABLE 1V I Strength of Reac- 3020- Max. Ex, Resin Amt Amine used and amount formalde- Solvent used. tion, tion distill. No. used grs. hyde soln. and amt. temp time, temp., 1 andamt. 7 f0. hrs. 0.

882 Dlethylarnine, 146 grams 37%, 162 g.-. Xylene, 882 g--- -25 150 480 Diethylamlne, 73 gramsg.. Xylene, 480 g--. 22-30 24 152 633 do 30%, 100 g. Xylene, 633 g- 21-34 38 147 441 Dibutylamlne, 129 grams... g. Xylene, 441 g--- 25-37 32 149 480 do -d0 Xylene, 480 g--. 20-24 .149 633 do d0. Xylene, 633 gm. 18-23 24 150 882 Morpholine, 174 grams Xylene, 882 g 20-26 35 145 480 Morpholine, 87 grams. Xylene, 480 g; 19-27 24 156 Xylene, 633 g.-. 20-23 24 147 Xylene, 473 g--- 20-21 as 148 Xylene, 511 g- 10-20 30 14s Xylene, 665 g 20-26 24 150 Xylene, 441 20-22 31 147 Xylene, 480 g 20-24 36 148 0 grams Xylene, 595 g 23-28 25 145 90 (CE3)CHCH2)2NH, 361 grams Xylene, 441 g-. 21-23 24 151 480 (olntoonzomonoo(onalononmNn, 301 grams Xylene, 480 20-24 24 150 511 (C4HBOCHZCH(CH3)O(OH3)CHGHZ)2NH, 301 grams Xylene, 511 g--. 20-22 25 140 49s (ontoonlonzoonzonoonlonmlqn, 300 grams. Xylene, 498 g... 20-25 24 140 542 (GHQOCHiGHQOCHQOHgO ontonzlzNmaoa rams- Xylene, 542 g--- 28-38 30 142 .547. (CHaOCHyCHgOCH2CHzOCHzCHzhNH, 309 grams. Xylene, 547 25-30 20 148 441 (013,0onronzomonlonlonnmn, 245 grams Xylene, 441 g.-- 20-22 28 14a 4 595 @330 CIEIaCJEIzCHzCHrCHeCHz)2 H, g a s Xylene, 595 g'.-. 18-20 25 146 391 c1130 CHzCHgCHgCHaCHzGHflgNH', 98 grams 30%, g Xylene, 391 g--. 10-22 24 145 PART 7 formaldehyde. Condensate 1b employed as reactants The products obtained as herein described by reactions actions. Generally speaking, the reaction will proceed at 1 a satisfactory rate under suitable conditions without any catalyst at all.

' Employing polyepoxides in combination with a nonbasic reactant the usual catalysts include alkaline materials such as causticsoda, caustic potash, sodium methylate, etc. Other catalysts may be acidic in nature and are of the kind characterized by iron and tin chloride. Furthermore, insoluble catalysts such as clays or specially prepared mineral catalysts have been used. If for any reason the reaction does not proceed rapidly enough with the diglycidyl ether -or other analogous reactant, then a small amount of finely divided caustic soda or sodium methylate could be employed as a catalyst. The amount generally employed would be 1% or 2%. I

It goes without saying the the reaction can take place in an inert solvent,-i. e., one that is not oxyalkylationsusceptible. Generally speaking, this is-most' conveniently an aromatic solvent such as xylene or a higher boiling or the coal tar solvent,or else a similarhigh boilingaromatic M.

resin 2a and diethylamine. The amount of resin employed Was'882 grams; the amount of diethylamine employed was 146 grams; the amount of 37% formaldehyde .that the condensate, as :such is strongly basic. If desired, a small amount of an alkaline catalyst'could be added,

such as finely powdered caustic soda, sodium methylate, etc. If such alkaline catalyst is added it may speed up the reaction but it'also may cause an undesirable reaction, such as the polymerization of a diepoxide.

In any event, grams ofthe condensate dissolved in 105 grams of xylene were stirred and heated to 100 C., 17 grams of the diepoxide previously identified as 3A and dissolved in an equal Weight of xylene were added dropwise. An initial addition of the xylene solution carried the temperature to about 106 C. The remainder of diepoxide was added during approximately an hours time. During this period of time the temperature rose to about C. The product was allowed to reflux at a temperature of about. Cfusing aphase-separ'ating trap. A small amount of xylenewas removed by means of a phase-separating trap so the refluxing temperature "'27 rose gradually to' about a maximum of 180. C. The mixture Was then refluxed at 180 for approximately 4 hours until the reaction stopped and the xylene which had been removed during the reflux period was'returned to the mixture; A small amount of material was Withdrawn and the xylene evaporated on the hot plate in order to examine the physical properties. The material was a dark red viscous semi-solid. It was insoluble in water, it was insoluble in 5% .gluconic acid, and it was soluble in xylene, and particularly in a mixture of 80% xylene and 20%methanol. However, if the material was dissolved in an oxygenated solvent and thenv shaken with 5% gluconic acid it showed a definite tendency to disperse, suspend, or form a sol, and particularly in a xylene- TABLE VIII Probable Probable Resin conmol. wt. of Amt. of Amt. of number of Ex. No. densate reaction product, solvent, hydroxyls used product 'grs. grs. per molecule At times we have found a tendency .forian insoluble I "P f' 15 .12 2 1 2 ig g i g g glfifi 2 2332? mass to form or at least to obtalninclpient cross-linking Y; on d is Sim 16 i Baht or gelling even when the molalratio is in the order of 2 f I: il bu ye 0 ff P moles of resin to one of diepoxide. We have found this 0 W ecu prevlous h m e can be avoided by any one ofv the following procedures cedure slmflar to t at emPlPyed mt 6 use 0 g yclde or 5 0 or their equivalent. Dilute the resin or the diepoxide, methylglyclde as DXYalkYlatmg agentssee, for example, or both, with an inert solvent, such as xylene or the like. Part 1 of Patent 2,602,062 dated July 1952 In some instances an oxygenated solvent, such as the t0 De Gr0 t6- p. diethyl ether of ethyleneglycol may be employed. An-

Various examples obtained in substantlally the same other procedure which is helpful is to reduce the amount manner are enumerated in the following tables: of catalyst used, or reduce the temperature of reaction TABLE v Con- Diep- Time Max. Ex. den- Amt., oxide Amt., Xylene, Molar of reactemp., Color and physical state No. sate grs. used grs. grs. ratio tion, 0.

used hrs.

105 3A 17 122 2:1 5 180 Dark viscous semi-solid. 124 3A 17 141 2:1 0 190 Do. 108 3A 17 125 2:1 5 182 D0. 116 3A 17 133 211 6 190 Do. i 120 3A 17 123 2:1 6 185 Do. 159 3A 17 176 2:1 8 192 Dark solid. 141 3A 17 158 2:1 6.5 190 Dark viscous semi-solid. 177 3A 17 194 2:1 8 188 Dark solid. 164 3A 17 181 2:1 7 190 Dark viscous semi-solid. 173 3A 17 190 211 i s 100 Dark solid. Solubility in regard to all these compounds was subby adding a small amount of initially lower boiling stantially similar to that which was described in Exsolvent such as benzene, or use benzene entirely. Also,

ample 1c. we have found it desirable at times .to use slightlyless TABLE VI V l Con- Diep- Time Max. Ex. den- Amt, oxide Amt., Xylene, Molar of reactemp Color and physical state No. sate grs. used grs. grs. ratio tion, C.

used hrs.

1 lD. 1b 105 B1 27.5 1325 2:1 I 6 182 Dark viscoussemi-solid. 2D 5b 124 B1 27.5 151.5 2:1 6 190 Do. 3D 108 B1 27.5 135.5 2:1 6 185 Do. 4D 116 B1 27.5 143.5 2:1 6 190 Do. 5D. 10b 120 B1 27.5 197.5 2:1 7 195 Do. '6D 1211 159 B1 27.5 186.5 2:1 8 190 Dark solid. 7D 1311 141 B1 27. 5 168. 5 2:1 7 194 Dark viscous semi-solid. 8D 18!] 177 B1 27.5 204.5 2:1 8 190 Dark solid. 9D 19b 164 B1 27.5 191.5 2:1 8 188 Dark viscous semi-solid. 10D... 20!) 173 B1 27.5 200.5 2:1 8 200 Darks id. Solubility in regard to all these compounds was subthan apparently the theoretical amount of diepoxide, for stantially similar to that which was described in Exam instance to instead of The reason for ple 1c. 60 this fact may reside in the possibility that the molecular TABLE VII weight dimensions on either the resin molecule or the diepoxide molecule may actually vary from the true Probable Probable molecular weight by several percent. Resin conmol. vivt. of Am}. otf Arnt. of Eugnber ot 65 Previously the condensate has been depicted in a sim- 3:2 a 3113, g i 3313 1? plified form which, for convenience, may be shown thus:

cule

(Amine)CH (Resln)CI-I (Arnme) 2,440 2, 450 1,230 11 Following such simplification the reaction product 5:238 3:258 ijg With a polyepoxide and particularly a diepoxide, would ,660 2,675 1,345 11 70 be indicated thus: 2, 740 2, 705 1, 335 11 I 3, 520 s, 505- 1, 765 11 3,140 3,140 1,570 11 (Arnine)OH (Resin)OHAAmine) v 3,880 3, 900 1, 950 11 3,620 3,600 1, 790 12 a D. G. 3,800 3,800 1, 900 12 J 75 (Amine)CH (Resm)CH;(Amine) I as the 'der'nulsifying' agent of our process may centrations.

- [(Amine) CH2 (Amine) I /[D. o. [(Amine) oHnAminn] [(Resin)OH2(Resin)]\ no. ;[(Resin) CHz(Resin)] [.(Amine) CH (Amine)] Q r [mesimJ [n o.

All the above indicates the complexity of the reaction product obtained after treating the amine-modified resin condensate with a polyepoxide and particularly diepoxide as herein described.

"PART 8 "as "diluents. Miscellaneous solvents such as pine oil,

carbontetrac'hloridc, sulfur dioxide extract obtained in the "refining of petroleum, etc., may be employed as dilueiits. Similarly,'the material or'materials employed be admixed 'with -one or more of the solvents customarily used in v connection with conventional 'demulsifying agents. Moreover, said material or'materials may be used alone or "in 'admixture'with other suitable well-known classes of 'demulsifying agents.

It i s 'well known that conventional demulsifyingagents 'inay beused in'a water-soluble form, or in anoil-soluble fofin, "or in a form exhibiting both oiland wateri solubility. Sometimes they maybe used in a form which 'exliibits'relatively limited oil-solubility. Howeven'since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to' 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because du The product of thepresent invention, for example, the product of Example 1C, 20%;

A cyclohexylamine salt of polypropylated napthalene monosulfonic acid, 24%;

An ammonium salt of a polypr'opylated napthalene monosulfonicacid, 24%

A sodium salt-of oil-soluble mahogany petroleum .sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%; Isopropyl alcohol, 5 The above proportions are all weight percents.

PART 9 .The products herein described as such and prepared in accordance with thisinvention can be used as emulsifying agents, for oils, fats and waxes, as ingredientsin insecticide compositions, or as detergents and Wetting agents in the laundering, scouring, dyeing, tanning and mordanting industries. They may also be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Other uses include the-preparation or resolutionofpetroleum emulsions, whether of the waterin-oil type or -oil-in-water type. 1" hey may be .used as additives inconnection with other emulsifying agents; they may be employed to contribute hydrotro-pic effects; :they may 'be used as anti-strippers inconnection with asphalts; they may be used to prevent corrosion, particularly the corrosionof ferrous metalsfor-various purposes and particularly in connection with the production of oil and gas, and also in refineries where crude oil'is converted into various commercial products. The products may be used industrially to inhibit or stop micro-organic growth or other objectionable lower forms of life, such as the growth of algae, or the like; they maybe used to inhibit said reagents undoubtedly have solubility within such con- This same fact is true inregard to the material or materials of our invention when employed as-;demulsifying agents. p

The materials of our. invention, when employed as treating or demulsifyingagents, are used in the conventional way, a mple, 'in Patent 2,626,929, dated January 27, 1953, -''-Part 3, and reference is; made thereto for a description of conventional procedures of demulsifying, including batch, continuous, and down the-hole demulsification, the

process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat and allowing the mixture to stratify.

Asnoted above, the products herein described'may-be used not only vin diluted .form,l'but also may be used admixed withsome other chemicaldemulsifier. A mixture which illustrates such combination is the following:

well known to'the art, described, for ex-' the growth of bacteria, moles, etc.; they are valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils, and also to hydraulic brake fluids of the aqueous or nonaqueous type; some have definite anti-corrosive action. They may be used also in connection with otherprocesses where they are'injectedinto an oil .or gas'well for purpose of removing aimud sheath, increasing the ultimate flowof fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood Waters. They can also be used indry cleaners soaps.

'With regard to the-above statements, reference is made particularlyto the use of the materialsas such, or in the form of a salt; the salt form refers to a salt involving either one or bothbasic'nitrogen atoms. Obviously, the salt form involves a modification in which-the hydrophile character can be either'increased or decreased and, inversely, the hydrophobe character can'be decreased or increased. For example, neutralizing the product with practically any low mclal acid, such as acetic acid, hydroxyacetic acid, lactic acid, or nitric acid, .is apt to markedly increase 'thehydrophile efiect. --One may also use acids of the type in which R is a comparatively small alkyl radical, such as methyl, ethyl or propyl. The hydrophile effect may be decreased and the hydrophob'e 'eifec't increased by neutralization 'with a monocarboxy detergent-forming acid. 'Theseareacids whichhave at least 8 and not more 7 than '32 carbon atoms. They. are obtainedfrom higher fatty acids and include acids having generally 10 to. 18 carbon atoms. We" have found that a particularly valuable anti-corrosive agent can be obtained from any suitable resin and formaldehyde provided the secondary amine is dicyclohexylamine. The corrosion-inhibiting properties of this compound can be increased by neutralization with either oneor two moles of an oil-soluble sulfonic acid, particularly a sulfonic acid of the type known as mahogany sulfonic acid.

The oil-soluble sulfonic acids previously referred to may be synthetically derived by sulfonating olefins, aliphatic fatty acids, or their esters, alkylated aromatics or their hydroxyl derivatives, partially hydrogenated aromatics, etc., with sulfuric acid or other sulfonating'agents. However, the soaps of so-called mahogany acids which are usually produced during treatment of lubricating oil distillates with concentrated sulfuric acid (85% or higher concentration) remain in the oil after settling out sludge. These sulfonic acids maybe represented as V 7 (It). son;

where (R),, is one or more alkyl, alkaryl or aralkyl groups and the aromatic. nucleus may be a single or condensed ring or a partially hydrogenated ring. The lower molecular weight acids can be extracted from the acid treated oil by adding a small amount of water, preferably after dilution of the oil with kerosene. the more desirable high molecular weight (350-500) 'acids, particularly those produced when treating petroleum distillates with fuming acid to produce Whole oil, are normally recovered as sodium soaps by neutralizing the acid oil with sodium hydroxide or carbonate and extracting with aqueous alcohol. The crude soap extract is first recovered as a Water curd after removal of alcohol by distillation and a gravity separation of some of the contaminating salts (sodium carbonate, sulfates and sulfites). These 'materials still contain considerable quantities of salts and consequently are normally pu ified by addition of a more concentrated alcohol followed by storage to permit settling of salt brine; The alcohol and water are then stripped out and so obtained converted into free acids. 7

Not only'can one obtain by-product sulfonic acids of the mahogany type which are perfectly satisfactory and within the molecular range of 300 to 600 but also one can obtain somewhat similar materials which areobtained as the principal product of reaction and have all the usual characteristics of normal by-product sulfonic acids but in the sodium salts some instances contain two sulfonic groups, i. e., are disulfonic acids. This type of mahogany acid,.or better still, oil-soluble sulfonic acid, is perfectly satisfactory for the above described purpose.

Much ofwhat has been said previously is concerned with derivatives in which the hydrophile properties are enhanced in comparison with the resin as, such. A procedure designed primarily to enhance the hydrophobe properties of the resin involves derivatives obtained by a phenyl or substituted phenyl glycidyl ether of the structure which'as suchgor in the form of the free base or hydrate,

However,

i. e., combination of water or particularly in the form of a low molal organic acid such as the acetate or bydroxyacetate, have sufficiently hydrophile character to at least meet the test set forth in U. S. PatentNo. 2,499,368, dated March 7, 1 950, to De Groote et al.- In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described. as an indexof surface activity.

Having thus described our invention, what we claim as new and desire .to secure by Letters Patent is:

1. The method of (A) condensing (a) an oxyalkyladon-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula lowed by (B) reacting said resin condensate with a.

phenolic polyepoxide free from reactive functional groups other than epoxy and hydroxyl groups and 'cogenerically associated compounds formed in the preparation of said polyepoxides; said epoxides being monomers and low molal polymers not exceeding the'tetramers; said polyepoxides being selected from the class consisting of (aa) compounds Where the phenolic nuclei are directly joined Without an intervening bridge radical, and (bb) compoundscontaining a radical in which 2 phenolic nuclei are joined by a divalent radical selected from the class 7 consisting of ketone residues formed by the elimination of the ketonic oxygen atom, and aldehyde residues obtained by'the elimination of the aldehyde oxygenfatom,

' the divalent radical the divalent o radical, thedivalent sulfone radical, and thedivalent monosulfideradical S-, the divalent radical v and the divalent disulfide radical 4+; said phenolic in which R, R, and R'" representa member of the class consisting of hydrogen and 'hydrocarbon'substitucnts'of the aromatic nucleus, said substituent member 33 7 having not over 18 carbon atoms; with the further provisothat said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be approximately 2 moles of the resin condensate per mole of the phenolic polyepoxide.

2. The method of (A) condensing (a) an oxyalkylation-susc eptible, fusible, non-oxygenated organic solventsoluble water-insoluble, low-stage phenol-aldehyde resin having an average molecular Weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by (B) reacting a phenolic diepoxide free from reactive functional groups other than epoxy and hydroxyl groups, and cogenerically associated compounds formed radical H H H H the divalent 1L radical, the divalent sulfone radical, and the divalent monosulfide radical --S-, the divalent radical --cH scH,,'

divalent disulfide radical S-S--; said phenolic portion of the diepoxide being obtained from a phenol of the structure in which R, RT, and R represent a member of the of the aromatic nucleus, said substituent member having not over 18 carbon atoms; the molar ratio of reactant (A) to reactant (B) being approximately 2 to 1 respectively; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

3. The method of (A) condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin.having an average molecular Weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol;

said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by (B) reacting a member of the class consisting of (aa) compounds of the following formula:

in which R represents a divalent radical selected from the class consisting of ketone residues formed by the elimination of the ketonic oxygen atom and aldehyde residues obtained by the elimination of the aldehydic oxygen atom, the divalent radical the divalent i radical, the divalent sulfone radical, and the divalent monosulfide radical -S-, the divalent radical CH SCH and the divalent disulfide radical -SS; and R 0 is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol in which R, R", and R' represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having 7 number not greater than 3; and (bb) cogenerically associated compounds formed in the preparation of (an) preceding, including monoepoxides; the molar ratio of reactant (A) to reactant (B) being approximately 2 to 1 respectively; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and resultants of reaction. I

4. The method of (A) condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature suficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by (B) reacting a member of the class consisting of (aa) compounds of the following formula wherein R is an aliphatic hydrocarbon bridge, each 11' independently has one of the values 0 to 1, and R is an alkyl radical containing from 1 to 12 carbon atoms, and (bb) cogenerically associated compounds formed in the preparation of (aa) preceding, including monoepoxides; with the proviso that (B) consist principally of the monomer as distinguished from other-cogeners; the molar ratio of reactant (A) to reactant (B) being approximately 2 to 1 respectively; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of solventsoluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

5. The'method of (A) condensing (a) anoxyalkylationsusceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight'corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming 335 a reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifun-ctional phenols; said phenol-being of theformula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with theproviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible;- followed by (B) reacting a member of the'class consisting of (aa) compounds of the following formula:

and (bb) cogenerically associated compounds formed in the preparation of (aa) preceding, including monoepoxides: with the proviso that (B) consist principally of the monomer as distinguished from other cogeners; the molar ratio of reactant (A) to reactant (B) being approximately 2' to 1 respectively with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solventsoluble liquids and low-melting solids; with the final proviso that thereaction product be a member of the class of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the *resultants of reaction.

6. Themethod of claim 1 whereinthe precursory phenol contains at least 4 and not over 14 carbon atoms in the substituent radical. V

7. The method of claim 1 wherein the precursory phenol contains at least 4 and not over 14 carbon atoms in the substituent radical and the precursory aldehyde is formaldehyde. 7

8. The product obtained by the method described in claim 1.

9. The product obtained by the method described in claim 2.

10. The product obtained by the method described in claim 3.

11. The product obtained by the method described in claim 4. l

12. The product obtained by the method described in claim 5.

13. The product obtained by the method described in claim 6. v

14. The product obtained .by the method described in claim 7.

References Cited in the file of this patent UNITED STATES'PATENTS 2,521,911 Greenleei Sept. 12, 1950 2,743,251 .De Gr'oote Apr. 24, 1956 

1. THE METHOD OF (A) CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENTSOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING ASN AVERAGE MOLECULAR WEIGH T CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOLFORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 